Process for applying gelled compositions of fungicides



United States Patent 3,253,984 PROCESS FOR APPLYING GELLED COMPOSI- TIONS OF FUNGICIDES Keith G. Seymour and Billy G. Harper, Lake Jackson,

Tex., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Mar. 18, 1965, Ser. No. 440,926 3 flaims. (Cl. 16742) This application is a continuation-in-part of patent application Serial No. 93.013, filed March 3, 1961, now US. Patent No. 3,176,898.

This invention relates to agricultural chemistry and more particularly is concerned with various aqueous mixtures whereby reduced drift loss of aqueous soluble and dispersible fungicides is accomplished in applications of such chemicals.

Generally, biologically active chemicals are applied in agricultural applications through the use of portable spray mechanisms, e.g., ground and aerial spray applicators. However, because of potential damage to adjacent areas through wind drift of the sprayed particles, economical aerial spray techniques can be carried out in many areas only when certain specified atmospheric conditions prevail.

In certain areas, predominantly the west, where checkerboard agriculture is the pattern, this spray drift problem is acute. The seriousness of the problem is emphasized by the existence of laws in many States control-ling the use and application of agricultural and horticultural sprays and insecticides.

Many attempts have been made to solve this problem.

Changes have been made in the design of spray nozzles and additives have been used in the attempt to prevent the production of extremely fine particles. The use of additives which thicken the solution, such as Carbapol, a trademarked polycarboxylic acid product made by B, F. Goodrich Co., and carboxymethyl cellulose, however, do not effectively inhibit the production of fine particles by the nozzle.

Another attempt at solving this problem, which has met with some success, is the formation of an invert emulsion. However, there is some difiiculty encountered in making such emulsions of the right consistency and the coverage is not as complete as desired whena biologically active chemical is applied in this way. It is to minimize drift during application that the present invention is directed.

It is a principal object of the present invention to reduce the application loss normally encountered because of wind drift of sprayed aqueous solutions of fungicides. Another object of the present invention is to provide an aqueous solution or dispersion of such agricultural chemicals in combination with a swellable polymer whereby substantially reduced drifting of its spray is accomplished. An additional object of the present invention is to provide a composition containing a fungicidal commodity which can be successfully administered by aerial application and which does not suffer appreciable spray drift during administration. Other objects and advantages will become apparent hereinafter.

The foregoing and additional objects are accomplished by providing an aqueous dispersion containing an effective quantity, i.e. a fungicidally effective amount, of a water dispersible or water soluble fungicide and containing from about 0.10 to about 20 percent by weight or more of a substantially water-insoluble, water-swellable, crosslinked polymer.

Preferably, crosslinked monovalent cation salts of polyacrylic acid, polyacrylamide, or copolyrners of acrylamide and acrylic acid are utilized as gelling agents for these solutions and dispersions. With the copolymers of acrylamide and acrylic acid ordinarily compositions containing from about 60 to about 75 weight percent of the acrylamide moiety and from about 40 to about 25 weight percent of acrylic acid constituent are used. Preferably when the copolymer is employed as gelling agent a copolymer of about percent by weight acrylamide and about 30 percent by weight acrylic acid is used. Any crosslinked polymer whose linear analogue is watersoluble can be used, e.g., crosslinked polyglycols having average molecular weights of from about 1000 up to a million or more, cross-linked substantiallywater-insoluble, water-swellable, sulfonated alkaryl and aromatic polyrners, for example, cross-linked sulfonated polyvinyl toluene, and copolymers of such sulfonated alkaryl and aromatic materials with acrylonitrile, alkylacrylonitriles and methacrylates and other crosslinked water-swellable polymers can be employed.

The substantially water-insoluble, water-swellable, cross-linked polyacrylate salts as used in the present invention are prepared by chemical cross-linking as shown in British Patent 719,330 or by subjecting a mixture of a monovalent cation salt of acrylic acid and water to the influences of high-energy ionizing radiation for a period of time sufiicient to effect the desired polymerization and the crosslinking of at least a portion of the polymer produced. Generally speaking, the amount of ionizing radiation should be at least 0.5 megarad but greater orlesser amounts may be employed. In any event, the amount of radiation must be great enough to give a swellable polymer which takes in water or aqueous solutions and in so doing increases in volume, but which generally retains its original shape. It is critical to the present invention that the salt-forming cation of such polyacrylate. resin be monovalent. Representative examples of monovalent cations include, for example, the alkali metals, i.e., sodium, potassium, lithium, rubidium and cesium, as well as Water soluble ammonium and ammonium-like radicals based upon the quaternary nitrogen atom.

While aqueous fungicidal dispersions and solutions containing as low as 0.10 percent based on the weight of the dispersion or solution, of the cross-linked alkali polyacrylate salt or acrylamide and acrylic acid copolyrners will show some improvement in spray drift loss of the sprayable aqueous dispersions, it is preferred to use quantities of from about 0.2 to 10.0 percent base on the weight of the dispersion. The amount to be employed in a given instance will depend upon the kind and amount of pesticide to be used. In any event, the amount of crosslinked, water-swellable water-insoluble polymer should be used such that a dispersion results which contains no substantial amount of free liquid. The dispersions, made up of discrete, elastic particles which do not coalesce on contact, are conveniently characterized by the term granular liquid. Thus, the dispersions of this invention form a particulate, gelled mass which contain substantially no free liquid.

In the procedure of the present invention, an aqueous solution or dispersion of a water soluble or water-dispersible fungicide is provided and a crosslinked polyacrylate salt, a homopolymer of acrylamide or a copolymer of acrylamide and acrylic acid is mixed with this to provide a swelled-gel. Generally, this mixing is accomplished by merely adding the resin to the aqueous dispersion with agitation, provided that the agitation is not of sufiicient magnitude to cause significant shearing of the polymer to particle sizes lower than about 0.05 mm. diameter. Advantageously, the gelled solutions can be prepared by first pulverizing the polymer to a desired particle size, such as will produce a swelled particle within the range of about .05 mm. to about 1.0 mm. in diameter, and then mixing the so-prepared powder into the aqueous solution with 3 stirring. It is understood that the amount of swellingof the particles is dependent upon the particular polymer employed and the extent to which the polymer is crosslinked.

Alternatively, chunks of the polymer can be added to an aqueous solution or dispersion of the fungicide. This produces a gel-like mass as the polymer swells. This mass then can be broken up by vigorous stirring to give a gel structure of discrete gelled particles the same as are obtained by adding the pulverized polymer to the aqueous solution.

Another variable which provides still a third alternative of gel preparation is the spray equipment itself. The size of the spray nozzle and the atomizing pressure on it can be varied so that the sprayed particles are sheared to the proper range of sizes while passing through the nozzle. Here the sprayer itself may act also as the stirring device.

The discrete, swelled polymer particles which make up the gel structure of this invention hold the dispersion of chemical. Since the fungicide is integrally bound by the gel structure, it is carried with the gel particles through the spray system and onto the sprayed surface. Advantageously, the sprayed particles are kept within a certain size range of from about 0.05 mm. to about 1.0 mm. and more particularly between about 0.12 mm. and 1.0 mm. although sprayed particles of somewhat larger diameter may be utilized in certain applications. Quantities of water dispersible fungicide to be employed are those quantities wihch are effective. By this is meant those quantities which would normally be employed in using such biologically active compositions of the prior art for control and/ or destruction of fungi since the compositional matter of the present invention usually does not affect the biological activity of the active compound. Understandably, it is essential that the compatibility of the fungicide formulation and the polymer used be considered in the utilization of the invention.

Of course, an admixture of appropriate proportions of a suitable unswelled polymer with a suitable fungicide has utility since this substantially dry mix can be added to Water to achieve the results of the present invention.

An unclassified particulate cross-linked polymer resin can be mixed with the fungicide and this mixture then added to water. Alternatively and advantageously the resin first can be screened to a desired particle size; the so-classified polymer can be mixed with the fungicide; and, this mixture then can be placed in water, preferably with stirring, to give the fungicide in a gelled dispersion of preselected swelled particle size.

In these dry mixtures, it is to be understood that the amount of the water-swellable, Water-insoluble, crosslinked polymer in the dry mixture is such that the gelled dispersion as produced in water contains from about 0.1 to about 20 weight percent of the dispersion weight of the resin.

The amount of the fungicide in the dry mixture isa predetermined effective quantity shown to produce the desired fungicidal result upon application of the resulting dispersion.

Additionally, if desired, surface active agents, wetting agents and dispersion promoters can be incorporated into the blend to promote wetting and correspondingly to more readily disperse the aqueous insoluble fungicides throughout the gelled product resulting from mixing the dry blend and water.

The following example is given to illustrate the present invention but is not to be construed as limiting the invention thereto.

- EXAMPLE An evaluation of spray drift-control of N-trichlorornethylmercapto 4 cyclohexened,2-dicarboximide fun- ;gicide was carried out as follows:

A box-like wind tunnel structure about 8 feet long, 4 feet wide, 6 feet high at one end and feet high at the other end was fitted with a variable speed fan in the end wall at the 6 foot high end of the box. At the opposite end of the box, a channel extended upwardly at right angles from the top of the box. A spray nozzle was located in the upper end of this channel. A bafiie was positioned within the channel just below the nozzle. This baffle was adjustable to assure that a uniform spray pattern passed into the air stream substantially in the center section (with respect to the side walls) of the box.

Both ends of the box were open and were fitted with horizontal and vertical vanes. These vanes assured that air turbulence was minimized and an air stream of uniform velocity passed through the box during operation.

In operation, an air stream of predetermined velocity was pulled through the box, this being controlled such that there was substantially no turbulence, particularly across the center section of the box into which the spray stream was fed. Spray was produced by forcing a liquid dispersion or solution through the spray nozzle by means of a pressurized inert gas, e.g. nitrogen pressure.

The distance that spray droplets drifted laterally along the length of the box before striking the bottom was indicative of the effectiveness of the gelling agent employed, i.e. an indication of spray drift control.

In a specific test with N-trichloromethylmercaptolcyclohexene-l,Z-dicarboxirnide, this fungicide, as a 50 percent active wettable powder was dispersed in water at a concentration of about 1.5 weight percent based on the active ingredient. About 83 grams of a dry, particulate copolymer of about 70 percent acrylamide and about 30 percent acrylic acid (-50 to mesh, US. Standard Sieve), said acid portion having been converted to the potassium salt, was stirred into about 12 liters of the aqueous fungicide dispersion. The resulting swelled-gel composition was a granular appearing mass which had substantially no free interstitial liquid between particles. The particle size of the resulting particulate swelled gel ranged from about 0.3 to about 1 millimeter in diameter.

As a control, a second aqueous fungicide solution was prepared using the same concentration of the active component but to which no gelling agent was added.

The resulting dispersions in separate duplicate tests were sprayed under a nitrogen pressure of about 20 pounds per square inch gage into the wind tunnel box. The air velocity through the box for both of the runs was maintained at 4 miles per hour.

Strips of Mylar polyethylene terephthalate resin (1.5 inches wide) were placed across the floor of the wind tunnel at distances of 3, 5 and 7 feet from a line on the floor drawn perpendicular to the side walls and directly below the nozzle. At 8 feet from this line, similarly sized strips of the Mylar resin were suspended across the box at 6 inches, 18 inches and 36 inches above the'floor.

Following the spray test, the strips were taken from the box, the sprayed droplets which impinged thereon were washed from the strips and the washings collected. The amount of fungicide present on each strip was determined by chemical analysis of the washings for the fungicide. The amount of fungicide found to be present on each strip in turn is a direct measure of the lateral drift of the spray along the length of the box.

Table 1, which follows, summarizes the results of the present study.

Table 1 Distance of Strip from Gelled Dispersion Aqueous Disper- Line Below Nozzle (feet) of Fungieide (mg. sion of Fungieide fungicide/strip) (control) (mg. tungicide/strip) Av. Av.

These results clearly show the marked reduction in spray drift provided by the gelled dispersion when employed in the present novel process.

In a manner similar to that of the foregoing example, other copolymers of acrylic acid and acrylamide or homopolymers of these materials as Well as monovalen-t salts of polyacrylic acid may be substituted for the copolymer of acrylic acid and acrylamide specifically shown. Ammonium, sodium, potassium, rubidium, cesium, methylamm-onium, ethylammonium, dimethylammonium, etc., salts of polyacrylic acid can be used as gelling agents with similar results obtained as for those obtained with the depicted copolymer. Also other fungicides such as ferric dimethyldithiocarbamate and zinc ethylene bisdithiocarbamate for example and the like may be employed with similar results. Further, other water-insoluble, water-swellable, cross-linked polymers, e.g., sulfonated crosslinke-d polyvinyltoluene, and crosslinked copolymers of such sulfonated alkaryl and aromatic materials with acrylonitrile, alkylacrylonitriles and methacrylates and other like crosslinked water-insoluble water-swellable polymers may be substituted for those polymers specifically shown with similar results. Any of the crosslinked, water-swellable, substantially Water insoluble polymers as herein suggested can be used as a gelling agent with aqueous dispersions of any fungicide.

Various modifications can be made in the present invention without departing from the spirit and scope thereof, for it is understood that we limit ourselves only as defined in the appended claims.

We claim:

1. A method for reducing spray drift in applying a fungicide Which comprises spraying a fungicidally effective amount of a fungicidal gel, said gel produced by mixing an aqueous dispersion containing a fungicidally effective amount .of a fungicide with a sufiicient amount of a crosslinked, water-swellable, water-insoluble polymer to provide a particulate, gelled dispersion of discrete, elastic, non-coalescent particles of said polymer with said aqueous dispersion of said fungicide, said particulate, gelled dispersion having substantially no free liquid, the discrete particles of said gelled dispersion having an effective diameter of from about 0.05 to about 1.0 millimeter.

2. A method for reducing spray drift in applying aqueous dispersions of a fungicide to undesired fungi which fective diameter of from about 0.05 to about 1.0 millimeter.

3. A method for reducing spray drift in applying a fungicide which comprises spraying a fungicidally effective amount of a fungicidal gel, said gel produced by mixing an aqueous dispersion containing a fungicidally effective amount of a fungicide with from about 0.2 to about 10 percent, based on the weight of the total dispersion, of a particulate, crosslinked, water-swellable, water-insoluble, copolymer of acrylic acid and acrylamide, the acrylic acid portion of said copolymer having been converted to a mon'ovalent alkali salt, thereby producing an elastic, non-coalescent, particulate, sprayable gel of discrete, swelled gel particles having substantially no free liquid, said particles having an effective diameter of from about 0.05 to about 1.0 millimeter.

References Cited by the Examiner UNITED STATES PATENTS 2,442,588 6/1948 DAlelio 26078.5 2,625,471 1/1953 MOWry et al. 7l-1 2,651,883 9/1953 Hedrick et a1 711 X 2,651,885 9/1953 Hedrick et al 711 X 2,652,322 9/1953 Hendrick et al. 712.6 X 2,652,323 9/1953 Mowry et al 71-2.6 X 2,703,276 3/1955 Hedrick et al. 7l-1 2,810,716 10/1957 Markus 26078.5 2,951,753 9/1960 Groves 711 3,060,084 10/1962 Littler 71-2.2 3,062,634 11/1962 Talbert 712.3 X

FOREIGN PATENTS 758,019 9/1956 Great Britain.

JULIAN S. LEVITT, Primary Examiner. 

1. A METHOD FOR REDUCING SPRAY DRIFT IN APPLYING A FUNGICIDE WHICH COMPRISES SPARYING A FUNGICIDALLY EFFECTIVE AMOUNT OF A FUNGICIDAL GEL, SAID GEL PRODUCED BY MIXING AN AQUEOUS DISPERSION CONTAINING A FUNGICIDALLY EFFECTIVE AMOUNT OF A FUNGICIDE WITH A SUFFICIENT AMOUNT OF A CROSSLINKED, WATER-SWELLABLE, WATER-INSOLUBLE POLYMER TO PROVIDE A PARTICULATE, GELLED DISPERSION OF DISCRETE, ELASTIC, NON-COALESCENT PARTICLES OF SAID POLYMER WITH SAID AQUEOUS DISPERSION OF SAID FUNGICIDE, SAID PARTICULATE, GELLED DISPERSION HAVING SUBSTANTIALLY NO FREE LIQUID, THE DISCRETE PARTICLES OF SAID GELLED DISPERSION HAVING AN EFFECTIVE DIAMETER OF FROM ABOUT 0.05 TO ABOUT 1.0 MILLIMETER. 